Meta substituted benzoylamino anthraquinones and process of making same



' Patented Feb. 25, 193

UNITED, STATES PAT/ENTFOFFICE KURT H. MEYER, OF MANNHEIM, AND HEINRICH HOIPFF AND ARTHUR KRAUSE, OF LUDWIGSHAFEN-ON-THE-RHINE, GERMANY, ASSIGNORS, BY MESNE ASSIGNMENTS, TO GENERAL ANILINE WORKS, INC., OF- NEW YORK, N. Y., A CORPORATION 01' DELAWARE META SUBSTITUTED IBENZQYLAMINO ANTHRAQUINONES AND PROCESS OF MAKING SAME No Drawing. Application filed November 3, 1925, Serial No. 66,668, and in Germany February 16, 1925.

It is already known that anthraquinones containing one or more benzoyl-amino groups in alpha position possess the property of vat coloring matters.

-We have now found that vat coloring matters possessing specially valuable properties are formed in the alpha-benzoyl-amino-anthraquinone series by those hitherto unknown alpha-benzoyl-amino-anthraquinones which contain in a benzoyl group, or in more than one benzoyl group, a substituent in meta position. Such substituents, however, which would detract from the fastness of the vat dyestuffs, as for example free hydroxy or amino groups, nitroor cyano-groups, should not be present, but difficulty attackable substituents, for example alkyl groups etherified hydroxy groups, etherified mercapto groups and many others are suitable which are not altered in a reducing vat or on chlorination and which, for the sake of brevity, will be referred to as diificulty attackable groups in the following and in the claims.

The Vat dyestuffs made in accordance with our present invention possesses a very good aflinity to vegetable fibres, silk and similar materials andvproduce bright shades of excellent fastness to light.

The said dyestuffs can'be prepared by boiling an alpha-amino anthraquinone which may contain or be free from other substituents with the required quantity of a metasubstituted benzoyl-chlorid or benzoic anhydrid, or by heating a mixture of the aminoanthraquinone body and a meta-substituted benzoic acid in the presence of a suitable condensing agent such for example'as thionyl chlorid, phosphorus pentachlorid, zinc chlorid and others. 1 The following examples willserve to further explain some modes of carrying our invention into practice but our invention is not restricted to these examples. The parts are by weight.

' Ewample 1 I 938 parts of 1.4-diamino-anthraquinone, 340 parts of meta-methoxy benzoyl-chlorid and 2400 parts of nitrobenzene are boiled under a reflux cooler until no unaltered diamino-anthraquinone can be found any longer. The vat dyestufi is isolated in the a usual manner. It corresponds to the formula M ca and dyes cotton from a dark violet vat beau tiful red shades with a bluish tinge.

Other ethers of meta-oxy-benzoyl-chlorid, for example meta-ethox -benzoyl-chlorid can be employed in an analogous manner.

E trample 2 NIELCO,

. I in Q0118 b oogi I l. 5 diamino 4 hydroxy anthraquinone when condensed with meta-methoxyor ethoxy-benzoyl-chlorid in a similar manner gives a'full red, l.5-diamino-4-methoxy-anthraquinone and orange, diamino-anthrarufine a violet 'blue; and l-methoxyl-aminoanthraquinone a scarlet red. These coloring tively oonl,

O OO.N g H matters have the following formulae, respec- 00m mace-O NH.C0Q OOH:

OCLN

OCH

CO-N

and

v OCH: NRC-0O Example 3 i 238 parts of 1.4-diamino-anthraquinone, 2500 parts of nitro-benzene and 310 parts of meta-toluic acid chloridare boiled under a obtained corresponding to the formula CH3- 0 NHLCO-O I l 11.00% u v forms garnet red glittering leaflets and dyes cotton from a dark vviolet vat bluish red shades of excellent fastness.

-Ea'omipl J4 446 parts of 1--amino-anthraquinone and 17 0 parts of isophthalic acid are suspended in i 'Qoe it i (ll) reflux cooler until lA-diamino-anthrzalquin one is'no longer present. The vat dyestuifdyes cotton from a cherry red vat, bright lemon yellow shades of excellent fastness.

The following products can be obtained in an analogous manner.

Shade on cotton Color of Dyestufl! fromthe vat m-toluic acid (2 mol.) and Violet 1.5 s diamino anthraquinone (1 mol.)

Yellow m benzo l amino benzoic Yellow acid mol.) and 1.5-diamino anthraquinone (1 mol.)

1 thiophenol methyl ether- 3-carboxylic acid (2 mol.) and 1.5-diamino-anthraquinone (1 mol.)

Isophthalic acid (1 mol.) and 3-brom-1-amino-anthraquinone (2 mol.)

Isophthalic acid (1 vmol.) and 1-benzoyl-amino-4- amino anthraquinone (2 mol.)

Violet Brownish- Yellow Cherry red Lemon yellow Brown-vio- Red - let lsophthalic acid (1 mol.) Yellow and 1 -benzoyl -amino 5 amino anthraquinone (2 mol.)

Violet 5-methoxy-1 a -isophthalic acid (1 mol.) and l-aminoanthraquinone (2 mol.)

Diphenyl-m.m-dicarboxylic Cherry red Lemon yellow acid (1 mol.) and l-amlnoanthraquinone (2 mol.)

Cherryred Lemon yellow Diphenylm.m-dicarboxylic Yellow acid (1 mol.) and l-benzoyl amino 5 amino an thraquinone (2 mol.)

Diphenyl m.m'-dicarboxylic acid (1 mol.) and 1-benzoyl -amino- 4 amino an thraqninone (2 mol.)

Diphenyl-m.m'-dicarboxylic acid (1 mol. and 3-broml-am no-an raquinone (2 mol.)

Violet Brown-violet Cherry red Lemon yellow We claim:

1. As new articles of manufacture, vat coloring matters of the anthraquinone series representing an anthraquinone body, containing at least onebenzoyl-amino group in alpha position which group in the benzoyl radicle contains a difiicultly attackable substituent in meta position but is unsubstituted in para-position.

2. As new articles of manufacture, vat coloring matters of the anthraquinone series representing anthraquinone with two metaalkoxy-benzoyl-amino groups in alpha positions.

In'testimony whereof we have hereunto set our hand".

- KURT H. MEYER.

HEINRICH HOPFF. ABTHURKRAUSE.

Red 1 

